Golf balls having layers made from thermoplastic compositions containing nucleating agents

ABSTRACT

Golf balls containing at least one layer made from a thermoplastic composition comprising a benzenetrisamide nucleating agent are provided. The thermoplastic composition may be an ionomer or non-ionomer resin. Golf balls of various constructions may be made including two-piece, three-piece, and four-piece balls. The composition is used preferably to form a golf ball core having improved resiliency, durability, toughness, and impact strength.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to golf balls containing at least one layer made from a thermoplastic composition comprising a nucleating agent. More particularly, the nucleating agent is a benzenetrisamide compound. The composition may be used to form any layer in the golf ball structure such as, for example, a core, intermediate layer, and/or cover. Preferably, the composition is used to form an intermediate or cover layer having improved hardness.

2. Brief Review of the Related Art

Nucleating agents are commonly added to crystallizable thermoplastics, such as polyoelfins, to make products used in various industrial applications. The nucleating agent provides nucleating sites for the thermoplastic material to crystallize from the melt. In this manner, the nucleating agents help control the crystallization rate, crystal size, and other crystalline properties of the material. Films, sheets, molded parts, and other products having improved chemical and physical properties may be made from the crystallizable material. For example, nucleating agents may be added to a crystallizable polypropylene resin to make a film. The stiffness, surface hardness, and scratch-resistant properties of the resulting polypropylene films may be increased.

McCullough, Jr, et al., U.S. Pat. No. 5,362,782 discloses polypropylene impact copolymer compositions containing a nucleating agent such as 50 to 2000 ppm sodium benzoate. This increases the stiffness and notched Izod impact strength of the composition making it useful in the production of molded and extruded articles, shaped containers, and films having good clarity.

Chatterjee, U.S. Pat. No. 5,674,630 discloses polypropylene impact copolymer compositions containing a homopolymer phase of predominantly homopolymeric polypropylene, a copolymer phase of copolymerized ethylene and propylene, and a nucleating agent. The compositions have a rubber content (Fc) in the range of 25 to 45% by weight, a crystallization temperature in the range of 122° to 132° C., a melt flow in the range of about 7 to about 60 dg/min, and a ratio of the intrinsic viscosity of the copolymer phase to the intrinsic viscosity of the homopolymer phase of 1.4 to about 1.9. The polypropylene impact copolymer compositions may be used to form cast films.

In recent years, multi-piece solid golf balls have become more popular for several reasons, including, ease of manufacturing, material costs, ball properties, and ball playing performance. For example, a three-piece solid golf ball containing an inner core, at least one intermediate layer surrounding the core, and an outer cover is commonly used. The inner core is made commonly of a rubber material such as natural and synthetic rubbers, styrene butadiene, polybutadiene, poly(cis-isoprene), or poly(trans-isoprene). The intermediate and outer cover layeres are commonly made of a thermoplastic material such as ionomer resins, polyamides or polyesters; and thermoplastic and thermoset polyurethane and polyurea elastomers.

Ionomer resins are commonly used to form intermediate layers and outer covers. “Ionomers” generally refer to ionic copolymers of an olefin such as ethylene and a vinyl comonomer having an acid group such as methacrylic, acrylic acid, or maleic acid. The copolymers contain inter-chain ionic bonding as well as covalent bonding. Metal ions such as sodium, lithium, zinc, and magnesium are used to neutralize the acid groups in the copolymer. Commercially available ionomer resins are used in different industries and include numerous resins sold under the trademarks, Surlyn® (available from DuPont) and Escor® and Iotek® (available from ExxonMobil). Ionomer resins are available in various grades and identified based on the type of base resin, molecular weight, type of metal ion, amount of acid, degree of neutralization, additives, and other properties.

In recent years, golf balls made with ionomer resins have become more popular, because they help provide a “hard” ball having generally good durability, toughness, and impact-resistance. These harder balls are generally more resistant to the wear and tear caused by a golf club repeatedly striking the ball over time. Moreover, hard golf balls have a higher compression and players tend to achieve greater flight distance when using such golf balls. The “hard” balls tend to travel a farther distance than “soft” balls, which is particularly desirable when hitting the ball off the tee. However, high compression balls are relatively stiff and this may have a detrimental effect. Players tend to experience a harder “feel” when their club face makes contact with such golf balls. The player senses less control, and the harder ball tends to have low initial spin. The sensation of striking the ball is generally less natural and comfortable with “hard” golf balls versus “soft” golf balls. With a golf ball having a softer feel, the player can place a spin on the ball and better control its flight pattern. The softer golf ball feels more natural. The player senses more control, and the softer ball tends to have high initial spin. This is particularly desirable when making approach shots near a golf hole green. Skilled players can place a back-spin on such balls so that they land precisely on the green.

The resiliency or coefficient of restitution (“COR”) of a golf ball (or golf ball sub-component such as a core) means the ratio of a ball's rebound velocity to its initial incoming velocity when the ball is fired out of an air cannon into a rigid plate. The COR for a golf ball is written as a decimal value between zero and one. A golf ball may have different COR values at different initial velocities. The United States Golf Association (USGA) sets limits on the initial velocity of the ball so one objective of golf ball manufacturers is to maximize the COR under these conditions. Balls (or cores) with a higher rebound velocity have a higher COR value. Such golf balls rebound faster, retain more total energy when struck with a club, and have longer flight distance. In general, the COR of the ball will increase as the hardness of the ball is increased. The test methods for measuring the COR are described in further detail below. In some conventional golf balls, materials are used to increase the hardness of the core so that the resiliency of the core is increased, and this, in turn, causes the compression of the core to increase.

It would be desirable to develop a cover or intermediate layer material that provides enhanced resiliency along with a soft feel to the golf ball. The material should have good durability, toughness, and impact strength. The material should have high resiliency and COR so that a player can drive the ball long distances. The material, however, should not be so stiff that playing performance properties such as feel, softness, and spin control are sacrificed. One objective of the present invention is to develop a material having an optimum combination of hard and soft properties. Improved resiliency, durability, toughness, and impact strength are some desirable hard properties, while a better feel and spin control are some desirable soft properties. The present invention provides a material and the resulting golf ball having these properties as well as other advantageous features and characteristics.

SUMMARY OF THE INVENTION

The present invention provides golf balls comprising an inner core, intermediate layer, and outer cover, wherein at least one layer is made of a thermoplastic composition containing a thermoplastic polymer and nucleating agent. The nucleating agent is a benzenetrisamide and is present in the amount of 0.001 to 5% by weight based on total weight of the composition. Suitable base thermoplastic polymers include, for example, ionomers; polyesters; polyamides; polyamide-ethers, and polyamide-esters; polyurethanes, polyureas, and polyurethane-polyurea hybrids; fluoropolymers; polystyrenes; polypropylenes and polyethylenes; polyvinyl chlorides; polyvinyl acetates; polycarbonates; polyvinyl alcohols; polyethers; polyimides, polyetherketones, polyamideimides; and mixtures thereof. Blends of ionomeric and non-ionomeric polymers may be used. The composition may further contain filler and pigments.

Golf balls made in accordance with this invention may have various constructions. The resulting golf ball has improved hardness hardness and resiliency without being overly stiff. Generally, the core has a surface hardness in the range of about 30 to about 65 Shore D; the cover has a material hardness in the range of about 30 to about 65 Shore D; and the intermediate layer has a material hardness in the range of about 30 to about 75 Shore D.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features that are characteristic of the present invention are set forth in the appended claims. However, the preferred embodiments of the invention, together with further objects and attendant advantages, are best understood by reference to the following detailed description in connection with the accompanying drawings in which:

FIG. 1 is a cross-sectional view of a three-piece golf ball having an intermediate layer made of a thermoplastic composition in accordance with the present invention;

FIG. 2 is a cross-sectional view of a three-piece golf ball having a cover made of a thermoplastic composition in accordance with the present invention; and

FIG. 3 is a cross-sectional view of a three-piece golf ball having an intermediate layer and cover made of a thermoplastic composition in accordance with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to golf balls having an intermediate and/or cover layer made from a thermoplastic composition comprising a thermoplastic polymer and nucleating agent, particularly a benzenetrisamide, as defined further below.

The term, “thermoplastic composition” as used herein, means a non-rubber composition (as defined below) comprising a thermoplastic polymer or polymer blend and benzenetrisamide nucleating agent that is thermoplastic in nature, particularly, it softens when exposed to heat and returns to its original condition when cooled to room temperature.

The term, “rubber composition” as used herein, means a composition having unique physical and chemical properties, particularly deformation (elongation) and elastic recovery after it has been cured or cross-linked with sulfur or other cross-linking agent.

The term, “polymer” as used herein, generally means any macromoleucle formed by linking together monomer units and includes homopolymers and copolymers.

Core Composition

The cores in the golf balls of this invention are typically made from rubber compositions containing a base rubber, a free-radical initiator agent, cross-linking co-agent, and fillers. The base rubber may be selected from polybutadiene rubber, polyisoprene rubber, natural rubber, ethylene-propylene rubber, ethylene-propylene diene rubber, styrene-butadiene rubber, and combinations of two or more thereof. A preferred base rubber is polybutadiene. Another preferred base rubber is polybutadiene optionally mixed with one or more elastomers selected from polyisoprene rubber, natural rubber, ethylene propylene rubber, ethylene propylene diene rubber, styrene-butadiene rubber, polystyrene elastomers, polyethylene elastomers, polyurethane elastomers, polyurea elastomers, metallocene-catalyzed elastomers, and plastomers. Particularly preferred base rubbers in compositions of the present invention are high Mooney polybutadienes. For purposes of the present invention, “high Mooney” refers to polybutadienes having a Mooney viscosity, as measured prior to oil or plasticizer addition, of 40 or greater. Preferred high Mooney polybutadienes of the present invention are neodymium-catalyzed, preferably having a cis content of 90% or greater, although low cis (<90%), trans, and vinyl versions are also suitable. Titanium-catalyzed, nickel-catalyzed, and cobalt-catalyzed high Mooney polybutadienes also are suitable.

The rubber composition is cured using a conventional curing process. Preferably, the cross-linked rubber composition is a thermoset rubber as opposed to a thermoplastic rubber such as an ethylene/propylene rubber, ethylene-propylene (EPDM) terpolymer or other modified polypropylene based-composition. In thermoplastic rubber compositions, the crystallization of the polypropylene segments causes cross-linking like behavior of the composition and this is reversible upon heating. Suitable curing processes include, for example, peroxide curing, sulfur curing, radiation, and combinations thereof. In one embodiment, the base rubber is peroxide cured. Organic peroxides suitable as free-radical initiators include, for example, dicumyl peroxide; n-butyl-4,4-di(t-butylperoxy)valerate; 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; di-t-butyl peroxide; di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoyl peroxide; t-butyl hydroperoxide; and combinations thereof. Peroxide free-radical initiators are generally present in the rubber compositions in an amount within the range of 0.05 to 15 parts, preferably 0.1 to 10 parts, and more preferably 0.25 to 6 parts by weight per 100 parts of the base rubber. Cross-linking agents are used to cross-link at least a portion of the polymer chains in the composition. Suitable cross-linking agents include, for example, metal salts of unsaturated carboxylic acids having from 3 to 8 carbon atoms; unsaturated vinyl compounds and polyfunctional monomers (e.g., trimethylolpropane trimethacrylate); phenylene bismaleimide; and combinations thereof. Particularly suitable metal salts include, for example, one or more metal salts of acrylates, diacrylates, methacrylates, and dimethacrylates, wherein the metal is selected from magnesium, calcium, zinc, aluminum, lithium, and nickel. In a particular embodiment, the cross-linking agent is selected from zinc salts of acrylates, diacrylates, methacrylates, and dimethacrylates. In another particular embodiment, the cross-linking agent is zinc diacrylate (“ZDA”). Commercially available zinc diacrylates include those selected from Rockland Reacr-Rite and Sartomer. When the cross-linking agent is zinc diacrylate and/or zinc dimethacrylate, the agent typically is included in the rubber composition in an amount within the range of 1 to 60 parts, preferably 5 to 50 parts, and more preferably 10 to 40 parts, by weight per 100 parts of the base rubber. When one or more less active cross-linking agents are used, such as zinc monomethacrylate and various liquid acrylates and methacrylates, the concentration of the less active cross-linking agent is the same or higher as the more active cross-linking agent (zinc diacrylate and zinc dimethacrylate).

Sulfur and sulfur-based curing agents with optional accelerators may be used in combination with or in replacement of the peroxide initiators to cross-link the base rubber. Suitable sulfur-based curing agents and accelerators include, for example, sulfur; N-oxydiethylene 2-benzothiazole sulfenamide; N,N-diorthotolylguanidine; bismuth dimethyldithiocarbamate; N-cyclohexyl 2-benzothiazole sulfenamide; N,N-diphenylguanidine; 4-morpholinyl-2-benzothiazole disulfide; dipentamethylenethiuram hexasulfide; thiuram disulfides; mercaptobenzothiazoles; sulfenamides; dithiocarbamates; thiuram sulfides; guanidines; thioureas; xanthates; dithiophosphates; aldehyde-amines; dibenzothiazyl disulfide; tetraethylthiuram disulfide; tetrabutylthiuram disulfide; and combinations thereof.

High energy radiation sources capable of generating free-radicals may also be used to cross-link the base rubber. Suitable examples of such radiation sources include, for example, electron beams, ultra-violet radiation, gamma radiation, X-ray radiation, infrared radiation, heat, and combinations thereof.

The rubber compositions may also contain “soft and fast” agents such as a halogenated organosulfur, organic disulfide, or inorganic disulfide compound. Particularly suitable halogenated organosulfur compounds include, but are not limited to, halogenated thiophenols. Preferred organic sulfur compounds include, but not limited to, pentachlorothiophenol (“PCTP”) and a salt of PCTP. A preferred salt of PCTP is ZnPCTP. A suitable PCTP is sold by the Struktol Company (Stow, Ohio) under the tradename, A95. ZnPCTP is commercially available from EchinaChem (San Fransisco, Calif.). These compounds also may function as cis-to-trans catalysts to convert some cis-1,4 bonds in the polybutadiene to trans-1,4 bonds. Peroxide free-radical initiators are generally present in the rubber compositions in an amount within the range of 0.05 to 10 parts and preferably 0.1 to 5 parts. Antioxidants also may be added to the rubber compositions to prevent the breakdown of the elastomers. Suitable antioxidants include, but are not limited to, quinoline type antioxidants, amine type antioxidants, and phenolic type antioxidants. Other ingredients such as accelerators (for example, tetra methylthiuram), processing aids, processing oils, dyes and pigments, wetting agents, surfactants, plasticizers, as well as other additives known in the art may be added to the composition. Generally, the fillers and other additives are present in the rubber composition in an amount within the range of 1 to 70 parts by weight per 100 parts of the base rubber. The core may be formed by mixing and forming the rubber composition using conventional techniques. These cores can be used to make finished golf balls by surrounding the core with outer core layer(s), intermediate layer(s), and/or cover materials as discussed further below.

Intermediate and Cover Layers

Referring to FIG. 1, one embodiment of a golf ball (10) is shown. The golf ball (10) may include at least one intermediate layer (12) made of the thermoplastic composition of this invention. As used herein, the term, “intermediate layer” means any layer of the ball disposed between the inner core (12) and outer cover (16). (In FIG. 1, the core (12) is made of a rubber composition as described above, while the cover (16) is made of a conventional thermoplastic or thermoset material.) The intermediate layer (14) may be considered an outer core layer or inner cover layer or any other layer disposed between the inner core (12) and outer cover (16) of the ball. The intermediate layer (12) also may be referred to as a casing or mantle layer. The ball may include one or more intermediate layers (12). Turning to FIG. 2, a different version of a golf ball (20) having a cover layer (24) made of the thermoplastic composition of this invention is shown. (In FIG. 2, the core (12) is made of a rubber composition as described above, while the intermediate layer (22) is made of a conventional thermoplastic or thermoset material.) Finally, in FIG. 3, a golf ball (30) having intermediate (32) and cover (34) layers made of the thermoplastic composition of this invention with an inner rubber core (12) is shown. It should be understood that the golf balls shown in FIGS. 1-3 are for illustration purposes only and not meant to be restrictive. Other golf ball constructions may be made in accordance with this invention.

Suitable thermoplastic polymers that can be used to form the intermediate and/or cover layers of the golf balls of this invention include, but are not limited to, partially- and fully-neutralized ionomers, graft copolymers of ionomer and polyamide, and the following non-ionomeric polymers: polyesters; polyamides; polyamide-ethers, and polyamide-esters; polyurethanes, polyureas, and polyurethane-polyurea hybrids; fluoropolymers; non-ionomeric acid polymers, such as E/Y- and E/X/Y-type copolymers, wherein E is an olefin (e.g., ethylene), Y is a carboxylic acid, and X is a softening comonomer such as vinyl esters of aliphatic carboxylic acids, and alkyl alkylacrylates; metallocene-catalyzed polymers; polystyrenes; polypropylenes and polyethylenes; polyvinyl chlorides and grafted polyvinyl chlorides; polyvinyl acetates; polycarbonates including polycarbonate/acrylonitrile-butadiene-styrene blends, polycarbonate/polyurethane blends, and polycarbonate/polyester blends; polyvinyl alcohols; polyethers; polyimides, polyetherketones, polyamideimides; and mixtures of any two or more of the above thermoplastic polymers.

Examples of commercially available thermoplastics include, but are not limited to: Pebax® thermoplastic polyether block amides, commercially available from Arkema Inc.; Surlyn® ionomer resins, Hytrel® thermoplastic polyester elastomers, and ionomeric materials sold under the trade names DuPont® HPF 1000 and HPF 2000, all of which are commercially available from E. I. du Pont de Nemours and Company; Iotek® ionomers, commercially available from ExxonMobil Chemical Company; Amplify® IO ionomers of ethylene acrylic acid copolymers, commercially available from The Dow Chemical Company; Clarix® ionomer resins, commercially available from A. Schulman Inc.; Elastollan® polyurethane-based thermoplastic elastomers, commercially available from BASF; and Xylex® polycarbonate/polyester blends, commercially available from SABIC Innovative Plastics. The additives and filler materials described above may be added to the intermediate layer composition to modify such properties as the specific gravity, density, hardness, weight, modulus, resiliency, compression, and the like.

The ionomeric resins may be blended with non-ionic thermoplastic resins. Examples of suitable non-ionic thermoplastic resins include, but are not limited to, polyurethane, poly-ether-ester, poly-amide-ether, polyether-urea, thermoplastic polyether block amides (e.g., Pebax® block copolymers, commercially available from Arkema Inc.), styrene-butadiene-styrene block copolymers, styrene(ethylene-butylene)-styrene block copolymers, polyamides, polyesters, polyolefins (e.g., polyethylene, polypropylene, ethylene-propylene copolymers, polyethylene-(meth)acrylate, polyethylene-(meth)acrylic acid, functionalized polymers with maleic anhydride grafting, and Fusabond® functionalized polymers commercially available from E. I. du Pont de Nemours and Company.

In one embodiment, the thermoplastic composition comprises a thermoplastic polymer selected from the group consisting of ionomers; polyesters; polyamides; polyamide-ethers, and polyamide-esters; polyurethanes, polyureas, and polyurethane-polyurea hybrids; fluoropolymers; polystyrenes; polypropylenes and polyethylenes; polyvinyl chlorides; polyvinyl acetates; polycarbonates; polyvinyl alcohols; polyethers; polyimides, polyetherketones, polyamideimides; and mixtures thereof.

As discussed above, it is critical that a nucleating agent be added to the thermoplastic composition of this invention. Of the many possible nucleating agents that can be used in the thermoplastic material, it was found that benzenetrisamides provide a composition having the most desirable properties for a golf ball layer made in accordance with this invention, In general, the benzenetrisamides have the following generic structure:

wherein R₁, R₂ and R₃ are identical and are cyclopropyl, cyclobutyl, cycloheptyl, 1-adamantyl, 3-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, S(+)-1-cyclohexylethyl, R(+)-1-cyclohexylethyl, isopropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2-butyl, 3-methylbutyl or 1,1,3,3-tetramethylbutyl.

Methods for making the benzenetrisamides are known in the art and described in such references as Schmidt et al., U.S. Pat. Nos. 7,235,191 and 7,479,515, the disclosures of which are hereby incorporated by reference.

As discussed above, it is a difficult task to prepare a thermoplastic composition containing a nucleating agent for use as an intermediate and/or cover layer in a golf ball. Adding a nucleating agent is difficult, because it tends to have both a positive and negative impact on the resulting thermoplastic composition. Particularly, the nucleating agent makes the composition more rigid. The stiffness and hardness of the composition are increased. On one hand, this is advantageous, because the golf ball tends to have enhanced COR. On the other hand, adding the nucleating agent may cause the thermoplastic composition to become overly stiff and this is disadvantageous. It is important the composition is not brittle. If the resulting intermediate and/or cover layer is too stiff, the golf ball may have a hard “feel.” With hard balls, the player senses less control when the club makes contact, and such balls feel less natural and comfortable. Moreover, if the ball is overly stiff, it is more difficult to control and place a spin thereon. Now, in accordance with the present invention, it has been found that the benzenetrisamides may be used to make a thermoplastic composition that, in turn, can be used to form an intermediate and/or cover layer having an optimum combination of properties. For purposes of this invention, the benzenetrisamides should be added in an amount of 0.001 to 5% by weight based on total weight of the composition. While not wishing to be bound by any theory, it is believed that adding the nucleating agent in this amount to the crystalline thermoplastic composition enhances the growth of preferred crystal polymorphs. The crystallites may exist above or below room temperature, may be transient or permanent, or may be induced during a mechanical deformation such as strain induced crystallization. These polymorphs enhance the resilience, durability, and toughness of the composition without making the composition overly rigid. The resulting ball tends to have sufficient hardness so that it has good resiliency as well as, durability, toughness, and impact strength. At the same time, however, the ball tends to have sufficient softness so that it has a soft feel and good spin control. In general, the golf ball has a COR value of about 0.60 to about 0.90 and a compression of about 70 to about 110.

The thermoplastic compositions of the present invention may include fillers to adjust the density, specific gravity, and/or other properties of the core. Examples of useful fillers for adjusting the density and specific gravity include metal or metal alloy powders, metal oxides, and carbonaceous materials. These include, but are not limited to, bismuth powder, boron powder, brass powder, bronze powder, cobalt powder, copper powder, iron metal powder, molybdenum powder, nickel powder, stainless steel powder, titanium metal powder, zirconium oxide powder, aluminum flakes, tungsten metal powder, beryllium metal powder, zinc metal powder, or tin metal powder. Examples of metal oxides include, but are not limited to, zinc oxide, iron oxide, aluminum oxide, titanium dioxide, magnesium oxide, zirconium oxide, and tungsten trioxide. Examples of particulate carbonaceous materials include, but are not limited to, graphite and carbon black. Examples of other useful fillers include but are not limited to graphite fibers, precipitated hydrated silica, clay, talc, glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate, zinc sulfide, silicates, diatomaceous earth, calcium carbonate, magnesium carbonate, regrind (which is recycled uncured center material mixed and ground to 30 mesh particle size), manganese powder, and magnesium powder. Other examples of useful fillers include polymeric, ceramic, metal, and glass microspheres.

Golf balls made in accordance with this invention can be of any size, although the USGA requires that golf balls used in competition have a diameter of at least 1.68 inches and a weight of no greater than 1.62 ounces. For play outside of USGA competition, the golf balls can have smaller diameters and be heavier. Preferably, the diameter of the golf ball is in the range of about 1.68 to about 1.80 inches. The core generally will have a diameter in the range of about 1.26 to about 1.60 inches. In one preferred version, the single-piece core has a diameter of about 1.57 inches. In general, core hardness is in the range of about 30 to about 70 Shore D and more preferably in the range of about 40 to about 60 Shore D. In FIGS. 1-3, the respective cores (12) are shown as single-piece structures made from a rubber composition. In other instances (not shown), a multi-piece core may be constructed; that is, there may be two or more core pieces made of the same or different rubber materials.

The range of thicknesses for the intermediate layer can vary, but it is generally in the range of about 0.015 to about 0.120 inches and preferably about 0.020 to about 0.060 inches. Multiple intermediate layers may be disposed between the inner core and outer cover. The thickness of the cover may vary, but it is generally in the range of about 0.015 to about 0.090 inches, preferably about 0.020 to about 0.050 inches, and more preferably about 0.020 inches to about 0.035 inches.

The golf balls of this invention may contain layers having the same hardness or different hardness values. The core generally has a hardness is in the range of about 30 to about 70 Shore D and more preferably in the range of about 40 to about 60 Shore D. The hardness of the intermediate and cover layers may vary, but each layer typically has a hardness in the range of about 30 to about 75 Shore D. The test methods for measuring hardness are described in detail below.

The golf balls of this invention may be constructed using any suitable technique known in the art. These methods generally include compression molding, flip molding, injection molding, retractable pin injection molding, reaction injection molding (RIM), liquid injection molding (LIM), casting, vacuum forming, powder coating, flow coating, spin coating, dipping, spraying, and the like.

The thermoplastic composition of this invention may be used with any type of ball construction known in the art. Such golf ball designs include, for example, single-piece, two-piece, three-piece, and four-piece designs. The core, intermediate (casing), and cover portions making up the golf ball each can be single or multi-layered depending upon the desired playing performance properties. As discussed above, in preferred embodiments, the thermoplastic composition of this invention is used in an intermediate and/or cover layer, each of which may be single or multi-layered. In other embodiments, the thermoplastic composition may be used into form a core. That is, the thermoplastic composition may be used in any golf ball construction so long as at least one layer comprises a thermoplastic composition prepared in accordance with this invention.

Test Methods

Hardness: The surface hardness of a golf ball layer (or other spherical surface such as a core) is obtained from the average of a number of measurements taken from opposing hemispheres, taking care to avoid making measurements on the parting line of the core or on surface defects such as holes or protrusions. Hardness measurements are made pursuant to ASTM D-2240 “Indentation Hardness of Rubber and Plastic by Means of a Durometer.” Because of the curved surface of the object, care must be taken to ensure that the golf ball or component (for example, a core) is centered under the durometer indentor before a surface hardness reading is obtained. A calibrated digital durometer, capable of reading to 0.1 hardness units, is used for all hardness measurements and is set to take the maximum hardness reading. The digital durometer must be attached to and its foot made parallel to the base of an automatic stand. The weight on the durometer and attack rate conforms to ASTM D-2240. It should be understood that there is a fundamental difference between “material hardness” and “hardness as measured directly on a golf ball.” For purposes of the present invention, material hardness is measured according to ASTM D2240 and generally involves measuring the hardness of a flat “slab” or “button” formed of the material. Surface hardness as measured directly on a golf ball (or other spherical surface) typically results in a different hardness value. The difference in “surface hardness” and “material hardness” values is due to several factors including, but not limited to, ball construction (that is, core type, number of cores and/or cover layers, and the like); ball (or sphere) diameter; and the material composition of adjacent layers. It also should be understood that the two measurement techniques are not linearly related and, therefore, one hardness value cannot easily be correlated to the other.

Compression: In the present invention, “compression” is measured according to a known procedure, using an Atti compression test device, wherein a piston is used to compress a ball against a spring. The travel of the piston is fixed and the deflection of the spring is measured. The measurement of the deflection of the spring does not begin with its contact with the ball; rather, there is an offset of approximately the first 1.25 mm (0.05 inches) of the spring's deflection. Cores having a very low stiffness will not cause the spring to deflect by more than 1.25 mm and therefore have a zero compression measurement. The Atti compression tester is designed to measure objects having a diameter of 1.680 inches; thus, smaller objects, such as golf ball cores, must be shimmed to a total height of 1.680 inches to obtain an accurate reading. Conversion from Atti compression to Riehle (cores), Riehle (balls), 100 kg deflection, 130-10 kg deflection or effective modulus can be carried out according to the formulas given in Compression by Any Other Name, Science and Golf IV, Proceedings of the World Scientific Congress of Golf (Eric Thain ed., Routledge, 2002) (“J. Dalton”).

Coefficient of Restitution (COR): In the present invention, COR is determined according to a known procedure, wherein a golf ball or golf ball subassembly (for example, a golf ball core) is fired from an air cannon at two given velocities and a velocity of 125 ft/s is used for the calculations. Ballistic light screens are located between the air cannon and steel plate at a fixed distance to measure ball velocity. As the ball travels toward the steel plate, it activates each light screen and the ball's time period at each light screen is measured. This provides an incoming transit time period which is inversely proportional to the ball's incoming velocity. The ball makes impact with the steel plate and rebounds so it passes again through the light screens. As the rebounding ball activates each light screen, the ball's time period at each screen is measured. This provides an outgoing transit time period which is inversely proportional to the ball's outgoing velocity. The COR is then calculates as the ratio of the ball's outgoing transit time period to the ball's incoming transit time period (COR=V_(out)/V_(in)=T_(in)/T_(out)).

It is understood that the golf balls described and illustrated herein represent only presently preferred embodiments of the invention. It is appreciated by those skilled in the art that various changes and additions can be made to such golf balls without departing from the spirit and scope of this invention. It is intended that all such embodiments be covered by the appended claims. 

1. A solid golf ball, comprising an inner core, an intermediate layer, and an outer cover, wherein the intermediate layer is formed from a thermoplastic composition comprising a thermoplastic polymer and nucleating agent, the nucleating agent being present in the amount of 0.001 to 5% by weight based on total weight of the composition and having the following structure:

wherein R₁, R₂ and R₃ are identical and are cyclopropyl, cyclobutyl, cycloheptyl, 1-adamantyl, 3-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, S(+)-1-cyclohexylethyl, R(+)-1-cyclohexylethyl, isopropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2-butyl, 3-methylbutyl or 1,1,3,3-tetramethylbutyl, the golf ball having a COR value of about 0.60 to about 0.90 and a compression of about 70 to about
 110. 2. The golf ball of claim 1, wherein the core comprises polybutadiene rubber.
 3. The golf ball of claim 1, wherein the thermoplastic composition comprises a thermoplastic polymer selected from the group consisting of ionomers; polyesters; polyamides; polyamide-ethers, and polyamide-esters; polyurethanes, polyureas, and polyurethane-polyurea hybrids; fluoropolymers; polystyrenes; polypropylenes and polyethylenes; polyvinyl chlorides; polyvinyl acetates; polycarbonates; polyvinyl alcohols; polyethers; polyimides, polyetherketones, polyamideimides; and mixtures thereof.
 4. The golf ball of claim 1, wherein the thermoplastic polymer is an ionomer.
 5. The golf ball of claim 1, wherein the thermoplastic polymer is a non-ionomer.
 6. The golf ball of claim 1, wherein the thermoplastic composition comprises a blend of ionomers and non-ionomers.
 7. The golf ball of claim 1, wherein the cover has a thickness in the range of about 0.015 to about 0.090 inches and a material hardness in the range of about 30 to about 65 Shore D.
 8. The golf ball of claim 1, wherein the intermediate layer has a thickness in the range of about 0.015 to about 0.120 inches and a material hardness in the range of about 30 to about 75 Shore D.
 9. A solid golf ball, comprising an inner core, an intermediate layer, and an outer cover, wherein the cover is formed from a thermoplastic composition comprising a thermoplastic polymer and nucleating agent, the nucleating agent being present in the amount of 0.001 to 5% by weight based on total weight of the composition and having the following structure:

wherein R₁, R₂ and R₃ are identical and are cyclopropyl, cyclobutyl, cycloheptyl, 1-adamantyl, 3-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, S(+)-1-cyclohexylethyl, R(+)-1-cyclohexylethyl, isopropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2-butyl, 3-methylbutyl or 1,1,3,3-tetramethylbutyl, the golf ball having a COR value of about 0.60 to about 0.90 and a compression of about 70 to about
 110. 10. The golf ball of claim 9, wherein the thermoplastic composition comprises a thermoplastic polymer selected from the group consisting of ionomers; polyesters; polyamides; polyamide-ethers, and polyamide-esters; polyurethanes, polyureas, and polyurethane-polyurea hybrids; fluoropolymers; polystyrenes; polypropylenes and polyethylenes; polyvinyl chlorides; polyvinyl acetates; polycarbonates; polyvinyl alcohols; polyethers; polyimides, polyetherketones, polyamideimides; and mixtures thereof.
 11. The golf ball of claim 9, wherein the thermoplastic polymer is an ionomer.
 12. The golf ball of claim 9, wherein the thermoplastic polymer is a non-ionomer. 